JPH02180624A - Manufacturing method of porous polymer membrane - Google Patents
Manufacturing method of porous polymer membraneInfo
- Publication number
- JPH02180624A JPH02180624A JP55289A JP55289A JPH02180624A JP H02180624 A JPH02180624 A JP H02180624A JP 55289 A JP55289 A JP 55289A JP 55289 A JP55289 A JP 55289A JP H02180624 A JPH02180624 A JP H02180624A
- Authority
- JP
- Japan
- Prior art keywords
- membrane
- porous
- layer
- polymer membrane
- dense layer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229920005597 polymer membrane Polymers 0.000 title claims abstract description 37
- 238000004519 manufacturing process Methods 0.000 title claims description 17
- 230000005855 radiation Effects 0.000 claims abstract description 3
- 239000011148 porous material Substances 0.000 claims description 29
- 150000002500 ions Chemical class 0.000 claims description 21
- 229920006254 polymer film Polymers 0.000 claims description 5
- 239000012528 membrane Substances 0.000 abstract description 49
- 238000000926 separation method Methods 0.000 abstract description 25
- 238000005530 etching Methods 0.000 abstract description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 abstract description 6
- 230000004992 fission Effects 0.000 abstract description 4
- 239000012286 potassium permanganate Substances 0.000 abstract description 3
- 238000001914 filtration Methods 0.000 abstract description 2
- 238000009751 slip forming Methods 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract description 2
- 238000010884 ion-beam technique Methods 0.000 abstract 1
- 238000000034 method Methods 0.000 description 9
- 238000010586 diagram Methods 0.000 description 8
- 229920000642 polymer Polymers 0.000 description 8
- 238000011282 treatment Methods 0.000 description 7
- 239000002245 particle Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 238000003486 chemical etching Methods 0.000 description 4
- 230000001678 irradiating effect Effects 0.000 description 4
- 239000012982 microporous membrane Substances 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000002657 fibrous material Substances 0.000 description 3
- -1 polytetrafluoroethylene Polymers 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 239000012634 fragment Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000010030 laminating Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000000108 ultra-filtration Methods 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000000020 Nitrocellulose Substances 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- FJWGYAHXMCUOOM-QHOUIDNNSA-N [(2s,3r,4s,5r,6r)-2-[(2r,3r,4s,5r,6s)-4,5-dinitrooxy-2-(nitrooxymethyl)-6-[(2r,3r,4s,5r,6s)-4,5,6-trinitrooxy-2-(nitrooxymethyl)oxan-3-yl]oxyoxan-3-yl]oxy-3,5-dinitrooxy-6-(nitrooxymethyl)oxan-4-yl] nitrate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](O[N+]([O-])=O)[C@H]1O[N+]([O-])=O)O[C@H]1[C@@H]([C@@H](O[N+]([O-])=O)[C@H](O[N+]([O-])=O)[C@@H](CO[N+]([O-])=O)O1)O[N+]([O-])=O)CO[N+](=O)[O-])[C@@H]1[C@@H](CO[N+]([O-])=O)O[C@@H](O[N+]([O-])=O)[C@H](O[N+]([O-])=O)[C@H]1O[N+]([O-])=O FJWGYAHXMCUOOM-QHOUIDNNSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000001413 cellular effect Effects 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 125000002573 ethenylidene group Chemical group [*]=C=C([H])[H] 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000001471 micro-filtration Methods 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229920001220 nitrocellulos Polymers 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 150000003109 potassium Chemical class 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000002285 radioactive effect Effects 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- BAZAXWOYCMUHIX-UHFFFAOYSA-M sodium perchlorate Chemical compound [Na+].[O-]Cl(=O)(=O)=O BAZAXWOYCMUHIX-UHFFFAOYSA-M 0.000 description 1
- 229910001488 sodium perchlorate Inorganic materials 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000001039 wet etching Methods 0.000 description 1
Landscapes
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
Description
【発明の詳細な説明】
Ｃ産業上の利用分野〕
本発明は、精密濾過膜や限外濾過膜等として利用しうる
新規な多孔性高分子膜の製造方法に関する。DETAILED DESCRIPTION OF THE INVENTION C. Industrial Application Field The present invention relates to a method for producing a novel porous polymer membrane that can be used as a microfiltration membrane, an ultrafiltration membrane, or the like.
従来、分離膜等に使用する微孔性の多孔膜は、機械的に
高分子膜（フィルム）又は繊維状物を（不完全）延伸す
る技術、化学的に高分子の溶解度差を利用する技術、ま
た、溶媒可溶の固体微粒子を混入後、溶出する技術、焼
結により多孔膜とする技術、気泡入り高分子シートの圧
潰による技術など従来公知の多孔化手段により製造され
ている。Conventionally, microporous membranes used for separation membranes, etc. have been produced using techniques that mechanically stretch polymer membranes (films) or fibrous materials (incompletely), and techniques that chemically utilize differences in solubility of polymers. It is also produced by conventionally known porous means such as mixing and eluting solvent-soluble fine solid particles, sintering to form a porous membrane, and crushing a cellular polymer sheet.
その多孔形態も三次元綱目状、独立気泡型、連通型など
不規則な有孔を有するもの、また、連続的に孔径が変わ
るなど種々様々にわたっている。The pore forms vary widely, including those with irregular pores such as three-dimensional mesh, closed cell, and open-cell types, as well as those with continuously changing pore diameters.
そして、その多孔膜中の見掛けの孔径も不均一であって
、対象とする被分離物の精製または除去の分離効率に限
界がある。Moreover, the apparent pore diameter in the porous membrane is also non-uniform, and there is a limit to the separation efficiency for purifying or removing the object to be separated.
機械的に（不完全）延伸したフィルムとして四弗化エチ
レン樹脂が知られているが、この膜は延伸により置引ト
けの孔径を制御しているため分離効率に限界がある。Tetrafluoroethylene resin is known as a mechanically (incompletely) stretched film, but the separation efficiency of this membrane is limited because the pore size during stretching is controlled by stretching.
また、化学的に処理された膜としてセルロースエステル
、ポリアミド、ポリスルホン等があり、これらの樹脂を
良溶媒に溶かした後、貧溶媒と接触させ多孔質膜を得る
溶解度差を利用するものがあるが、この構造は、多孔層
の上に緻密層または多孔質スキン層を存している。この
膜の孔径制御は、溶媒の種類、濃度、温度等を制御こと
によるもので、見掛けの孔径も不均一で、分離効率に限
界がある。In addition, there are chemically treated membranes such as cellulose ester, polyamide, and polysulfone, which utilize the difference in solubility to obtain porous membranes by dissolving these resins in a good solvent and then contacting them with a poor solvent. , this structure has a dense layer or a porous skin layer on top of the porous layer. The pore size of this membrane is controlled by controlling the type, concentration, temperature, etc. of the solvent, and the apparent pore size is nonuniform, which limits the separation efficiency.
近年、緻密な高分子フィルムにイオンを照射した後、損
傷部分を化学的にエツチングすることにより多孔膜が得
られることが明らかになっている。In recent years, it has become clear that porous membranes can be obtained by irradiating dense polymer films with ions and then chemically etching the damaged areas.
このような例として、特公昭５２−３９８７号公報、特
開昭５９４１７５４６号公報等に記載の技術が知られて
いる。As such examples, techniques described in Japanese Patent Publication No. 52-3987, Japanese Patent Application Laid-Open No. 59417546, etc. are known.
このようにして得られる分離膜は、均一な孔径が得られ
、分離効率が良い。The separation membrane obtained in this way has a uniform pore size and has good separation efficiency.
しかし、このような膜には、イオンが貫通するためのフ
ィルムの厚さが必要であり、工業用として市販されてい
るイオン加速器を利用する場合、イオンのエネルギーは
たかだか１０ＭｅＶ以下であって、膜厚に限界があり、
かつ利用できるイオン種、高分子に限りがある。また、
分離膜として利用する場合、強度を保持するために、最
低限厚みが１０μ攬以上必要であり、このようなフィル
ムを化学的にエツチングする場合には、多大な時間を要
する。さらに、このようにして得られる分離膜は、孔径
がフィルム方向に均一であり、且つ孔の長さが長いため
分離に要する時間も長（なる、即ち、分離に要する処理
時間が長くなる。However, such a membrane requires a thickness for the ions to penetrate, and when using a commercially available ion accelerator for industrial use, the energy of the ions is at most 10 MeV or less, and the film cannot penetrate through the membrane. There is a limit to the thickness,
Moreover, there are limits to the ionic species and polymers that can be used. Also,
When used as a separation membrane, the film must have a minimum thickness of 10 μm or more in order to maintain its strength, and chemically etching such a film requires a large amount of time. Furthermore, since the separation membrane thus obtained has uniform pore diameters in the film direction and long pore lengths, the time required for separation is long (that is, the processing time required for separation is long).
〔課題を解決するための手段］
本発明者らは、従来法により製造された三次元網目状な
ど微孔性多孔膜とイオン照射により製造された直孔型多
孔膜との製造技術を組合せることに着目し、予期せずし
て本発明を完成するに至った。[Means for Solving the Problems] The present inventors combined the manufacturing technology of a microporous membrane such as a three-dimensional mesh membrane manufactured by a conventional method and a straight porous membrane manufactured by ion irradiation. By paying attention to this, the present invention was unexpectedly completed.
すなわち、本発明は：
予め作成した微孔性の多孔膜にイオン照射した後、化学
的にエツチングすることを特徴とする、高効率分離能を
有する複合型多孔性高分子膜の製造方法である。That is, the present invention is: A method for producing a composite porous polymer membrane having high efficiency separation capability, which comprises irradiating a pre-prepared microporous membrane with ions and then chemically etching it. .
本発明の多孔性高分子膜の製造方法は、■緻密層（Ｂ）
及び微孔性の多孔層（Ａ）が連続して形成されている多
孔性高分子膜あるいは、■緻密層膜（Ｂ）を微孔性の多
孔膜（Ａ）に積層した多孔性高分子ｊ模を出発膜とし、
イオンを照射して緻密層に照射損傷を形成した後、化学
的にエツチングするものである。The method for producing a porous polymer membrane of the present invention includes: ■Dense layer (B)
and a porous polymer membrane in which a microporous porous layer (A) is continuously formed, or a porous polymer j in which a dense layer membrane (B) is laminated on a microporous membrane (A). Using the pattern as a starting film,
This method involves irradiating ions to form irradiation damage in the dense layer, and then chemically etching it.
本発明の多孔性高分子膜の製造に用いる多孔膜は、従来
公知の方法により容易に製造される。The porous membrane used for manufacturing the porous polymer membrane of the present invention can be easily manufactured by a conventionally known method.
例えば、■積層型の複合多孔膜の場合、高分子膜（フィ
ルム）を機械的に（不完全）延伸したり、また化学的に
高分子の溶媒への溶解度差を利用する等の公知の微孔化
方法により微孔性の多孔膜を形成する。次に、この多孔
膜に、高分子を溶解した溶液を塗布したり、高分子膜（
フィルム）をラミネートすることにより、微孔性の多孔
層と緻密層とを積層して多孔膜が得られる。For example, in the case of laminated composite porous membranes, well-known techniques such as mechanically (incompletely) stretching the polymer membrane (film) or chemically utilizing the difference in solubility of polymers in solvents are used. A microporous porous membrane is formed by a pore forming method. Next, a solution in which a polymer is dissolved is applied to this porous membrane, or a polymer membrane (
By laminating a microporous layer and a dense layer, a porous membrane can be obtained.
■また、連続型の多孔膜の場合、化学的に高分子への溶
解度差を利用する等の方法により、多孔質層と緻密層と
を連続的に形成して得られる。(2) In the case of a continuous porous membrane, it can be obtained by continuously forming a porous layer and a dense layer by chemically utilizing the difference in solubility in polymers.
このような、多孔膜にイオン加速器や核分裂片等の高エ
ネルギーのイオンを照射することにより、緻密層に照射
損傷を与える０次に、化学的にエツチングすることによ
り緻密層に孔径の均一な直孔型の孔を有し、その下層に
微孔性の多孔層を有する本発明の多孔性高分子膜が製造
できるのである。By irradiating such a porous film with high-energy ions from an ion accelerator or nuclear fission fragments, the dense layer is damaged by irradiation.The dense layer is then chemically etched to form a straight layer with uniform pore diameters. It is possible to produce the porous polymer membrane of the present invention, which has pore-shaped pores and a microporous layer underneath the pores.
この発明に用いる高分子膜としては、照射損傷と化学的
エツチング処理が適用されうる種々の高分子膜（フィル
ム）が挙げられ、具体的にはポリカーボネート、ポリエ
ステル、硝酸セルロース、酢酸セルロース、ポリ弗化ビ
ニリデン、ポリテトラフルオロエチレン、ポリアクリロ
ニトリル等の高分子膜（フィルム）が挙げられる。Examples of the polymer film used in this invention include various polymer films to which radiation damage and chemical etching treatments can be applied. Specifically, polycarbonate, polyester, cellulose nitrate, cellulose acetate, polyfluoride Examples include polymer membranes (films) such as vinylidene, polytetrafluoroethylene, and polyacrylonitrile.
本発明の多孔性高分子膜の製造に使用される微孔性の多
孔膜としては、機械的に高分子膜（フィルム）又は繊維
状物を（不完全）延伸する技術、化学的に高分子の溶解
度差を利用する技術、また、溶媒可溶の固体微粒子を混
入後、溶出する技術、焼結により多孔膜とする技術、気
泡入り高分子シートの圧潰による技術など従来公知の多
孔化手段により製造されるものが挙げられる。The microporous membrane used in the production of the porous polymer membrane of the present invention includes techniques for mechanically (incompletely) stretching a polymer membrane (film) or fibrous material, and techniques for chemically stretching a polymer membrane (film) or fibrous material. By using conventionally known porous means, such as technology that utilizes the solubility difference between solvents, technology that involves mixing and eluting solvent-soluble solid particles, technology that creates a porous membrane by sintering, and technology that involves crushing a bubble-filled polymer sheet. Examples include those that are manufactured.
本発明に用いられる高エネルギーイオン（粒子）として
は、高分子膜（フィルム）を貫通して所望の照射損傷を
形成しつる公知の種りの荷電、非荷電粒子を意味し、具
体的には、核分裂性物質の核分裂によって得られる核分
裂片、放射性同位元素の崩壊によって得られるα粒子及
び加速器によって得られる加速イオン等が挙げられるが
、この加速器による加速イオンを用いるのが工業上簡便
である。そのエネルギー域としては、ＩＭｅＶ以上が適
当である。The high-energy ions (particles) used in the present invention refer to various types of charged and uncharged particles known to penetrate a polymer membrane (film) and form desired irradiation damage. , fission fragments obtained by fission of fissile materials, α particles obtained by decay of radioactive isotopes, and accelerated ions obtained by an accelerator.It is industrially convenient to use accelerated ions produced by this accelerator. The appropriate energy range is IMeV or higher.
本発明に用いる化学的エツチング処理には、−般に、化
学処理エツチング剤に高分子膜（フィルム）を所定時間
浸漬させて行う、いわゆる湿式エツチング処理が好適に
通用できる。As the chemical etching treatment used in the present invention, a so-called wet etching treatment in which a polymer film is immersed in a chemical etching agent for a predetermined period of time is generally suitable.
使用する化学的エツチング剤としては、水酸化ナトリウ
ム、水酸化カリウム等のアルカリ溶液やクロム混酸、過
マンガン酸カリ、過塩素酸ナトリウム等の酸化剤や、硝
酸、硫酸、弗化水素酸等の酸性溶液が挙げられる。Chemical etching agents used include alkaline solutions such as sodium hydroxide and potassium hydroxide, oxidizing agents such as chromium mixed acid, potassium permanganate, and sodium perchlorate, and acidic agents such as nitric acid, sulfuric acid, and hydrofluoric acid. Examples include solutions.
本発明の製造方法により得られる多孔性高分子膜は、孔
径の均一な直孔型の多孔層（Ｂ）を有していて分離効率
が大きいと共に、微孔性多孔層（Ａ）にそれに対する支
持体的役割を果たさせているので、分子篩、水精製用な
ど精密濾過膜、限外濾過膜のような分離膜として極めて
有用である。The porous polymer membrane obtained by the production method of the present invention has a straight pore type porous layer (B) with uniform pore diameter and has high separation efficiency. Since it plays the role of a support, it is extremely useful as a separation membrane such as a molecular sieve, a precision filtration membrane for water purification, and an ultrafiltration membrane.
本発明の多孔性高分子膜の製造方法は、従来法により製
造された三次元網目状などの微孔性の多孔分離膜と、イ
オン照射により製造された直孔型の多孔分離膜の両者の
欠点を補完する製造技術に相当する。The method for producing a porous polymer membrane of the present invention can be applied to both microporous separation membranes such as three-dimensional mesh membranes produced by conventional methods and straight-pore porous separation membranes produced by ion irradiation. It corresponds to a manufacturing technology that compensates for deficiencies.
すなわち、分離膜の機械的強度を三次元網目状などの微
孔性の多孔層（Ａ）に持たせ、高効率分離をイオン照射
の直孔型多孔層（Ｂ）に持たせるように製造技術に工夫
を凝らした点にある。In other words, the manufacturing technology is such that the mechanical strength of the separation membrane is given to the microporous layer (A), such as a three-dimensional network, and the high efficiency separation is given to the ion-irradiated straight-pore porous layer (B). The point is that we have put a lot of effort into this.
本発明の製造方法により得られる多孔性高分子膜は、一
般のイオン照射による多孔性膜に比して、イオン照射多
孔層（Ｂ）を１０７７１１以下と極めて薄くすることが
でき、エツチングに要する時間が短縮でき、且つ得られ
た高分子膜は、被分離物を分離・除去する処理速度が早
くなるという、従来の多孔性高分子膜に見られない特徴
を有している。The porous polymer membrane obtained by the production method of the present invention can have an extremely thin ion-irradiated porous layer (B) of 107711 or less compared to a general porous membrane produced by ion irradiation, and the time required for etching can be made extremely thin. can be shortened, and the resulting polymer membrane has features not found in conventional porous polymer membranes, such as a faster processing speed for separating and removing substances to be separated.
本発明の製造方法により得られた多孔性高分子膜を添付
の図面によって説明する；
第１〜２図は、夫々連続一体化、積層化の本発明の多孔
性高分子膜の断面を示す略図である。The porous polymer membrane obtained by the production method of the present invention will be explained with reference to the accompanying drawings; Figures 1 and 2 are schematic diagrams showing cross sections of the porous polymer membrane of the present invention in continuous integration and lamination, respectively. It is.
第３〜４図は、従来例の多孔性高分子膜の断面を示す略
図である。3 and 4 are schematic diagrams showing cross sections of conventional porous polymer membranes.
第５図は、イオン照射、エツチング処理により得られた
従来例の多孔性高分子膜の断面を示す略図である。FIG. 5 is a schematic diagram showing a cross section of a conventional porous polymer membrane obtained by ion irradiation and etching treatment.
以上の各図面を対比して明らかなように、第１〜２図に
示される本発明の製造方法により得られた多孔性高分子
膜は、第３〜５図に示される従来例の多孔膜とは全く異
なって、直孔型の多孔層（Ｂ）と微孔性の多孔層（Ａ）
とを組み合わせたものであり、優れた分離機能を発揮し
うるものである。As is clear from comparing the above drawings, the porous polymer membrane obtained by the manufacturing method of the present invention shown in Figs. 1 and 2 is different from the porous polymer membrane of the conventional example shown in Figs. Completely different from the above, a straight-pore type porous layer (B) and a microporous porous layer (A)
It is a combination of the following, and can exhibit an excellent separation function.
本発明を下記の実施例により説明するが、これは本発明
の範囲を制限するものでない。The invention is illustrated by the following examples, which are not intended to limit the scope of the invention.
１廉斑
ポリ（２，６−シメチルー１．４−フェニレンエーテル
）をポリ（Ｎ−ビニルとロリドン）に溶解し、４０重量
％とした後、ガラス板上に塗布し、水中に浸漬して、厚
さ１ｍｍの多孔性分離膜を得た。1. Poly(2,6-dimethyl-1,4-phenylene ether) was dissolved in poly(N-vinyl and lolidon) to make 40% by weight, and then applied on a glass plate and immersed in water. A porous separation membrane with a thickness of 1 mm was obtained.
この膜のガラス板と接して方は多孔質層、また、最初に
水と接した方は緻密な層が形成されている。A porous layer is formed on the side of this membrane that comes into contact with the glass plate, and a dense layer is formed on the side that first comes into contact with water.
このとき形成される緻密層は１μｍ以下である。The dense layer formed at this time is 1 μm or less.
このようにして作成した分離膜にイオン加速器にてＨｚ
” イオンを緻密層側から照射した。照射条件は、加速
電圧１．ＯＭＶ、照射量Ｉ ＸＩＯ”／ｃ＋４である。The separation membrane created in this way is heated to Hz using an ion accelerator.
``Ions were irradiated from the dense layer side.The irradiation conditions were an acceleration voltage of 1.OMV and an irradiation amount of IXIO''/c+4.
得られた膜を、飽和過マンガン酸カリ水溶液で８０°Ｃ
の条件下で１０時間エツチングすることにより、緻密層
に均一な０．１ μｍの孔径を有する直孔型の孔が得ら
れ、三次元網目状などの微孔性多孔層と直孔層との分離
膜が得られた。The obtained membrane was heated at 80°C in a saturated potassium permanganate aqueous solution.
By etching for 10 hours under these conditions, straight pores with a uniform pore diameter of 0.1 μm were obtained in the dense layer, and the formation of a microporous layer such as a three-dimensional network and a straight pore layer was obtained. A separation membrane was obtained.
本発明の製造方法により得られた多孔性高分子膜は、孔
径の均一な直孔型多孔層を有しているので分離効率が太
き（、且つ三次元網目状などの微孔性多孔層が支持・補
強体としての役割を果たし、強度的にも優れた多孔膜を
与える。The porous polymer membrane obtained by the production method of the present invention has a straight pore type porous layer with uniform pore diameter, so it has a high separation efficiency (and has a microporous layer such as a three-dimensional network). plays the role of support and reinforcement, providing a porous membrane with excellent strength.
また、本発明の製造方法によると、直孔型多孔層となる
緻密層が１μｍ以下と極めて薄層とすることができ、加
速電圧１．ＯＭＶでもＮｔＩ イオンがこの層を貫通す
ることができ、従ってエツチング時間も短くてすむ効果
がある。Further, according to the manufacturing method of the present invention, the dense layer that becomes the straight porous layer can be made extremely thin at 1 μm or less, and the accelerating voltage 1. OMV also allows NtI ions to penetrate through this layer, which has the effect of shortening the etching time.
第１図は、緻密層を有する、見掛けの孔径が連続して変
化した一体型の多孔膜（第３図）の緻密層にイオン照射
後、エンチング処理により得られた、直孔型多孔層を有
する多孔性高分子膜（本発明）の断面を示す略図である
。
第２図は、従来の微孔性多孔層のみの高分子膜（第４図
）に緻密層を積層した後、イオン照射、エツチング処理
して得られた、直孔型多孔層を有する多孔性高分子膜（
本発明）の断面を示す略図である。
第３図は、緻密層を有する、見掛は孔径が連続して変化
した一体型の多孔性高分子膜（従来例）の断面を示す略
図である。
第４図は、微孔性の多孔層のみの高分子膜（従来例）の
断面を示す略図である。
第５図は、イオン照射後、エンチング処理により得られ
た、直孔型の多孔膜（従来例）の断面を示す略図である
。
１＝ 直孔型多孔層
２： 連続化多孔層
２゛： 多孔層
緻密層Figure 1 shows a straight pore type porous layer obtained by etching treatment after ion irradiation of the dense layer of an integrated porous membrane (Figure 3) with a dense layer and a continuous change in apparent pore diameter. 1 is a schematic diagram illustrating a cross section of a porous polymer membrane (invention) having a porous polymer membrane according to the present invention. Figure 2 shows a porous membrane with a straight-pore type porous layer obtained by laminating a dense layer on a conventional polymer membrane with only a microporous porous layer (Figure 4), followed by ion irradiation and etching treatment. Polymer membrane (
1 is a schematic diagram showing a cross section of the present invention). FIG. 3 is a schematic diagram showing a cross section of a monolithic porous polymer membrane (conventional example) with a dense layer and an apparently continuous change in pore size. FIG. 4 is a schematic diagram showing a cross section of a polymer membrane (conventional example) having only a microporous layer. FIG. 5 is a schematic diagram showing a cross section of a straight-hole type porous membrane (conventional example) obtained by etching treatment after ion irradiation. 1= Direct porous layer 2: Continuous porous layer 2゛: Porous layer dense layer
Claims (1)
高分子膜に、イオンを照射し緻密層に照射損傷を形成し
た後、化学的にエッチング処理することを特徴とする、
直孔型の孔を有する多孔性高分子膜の製造方法。A porous polymer film consisting of a microporous layer (A) and a dense layer (B) is irradiated with ions to form radiation damage in the dense layer, and then chemically etched.
A method for producing a porous polymer membrane having straight pores.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP55289A JPH02180624A (en) | 1989-01-06 | 1989-01-06 | Manufacturing method of porous polymer membrane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP55289A JPH02180624A (en) | 1989-01-06 | 1989-01-06 | Manufacturing method of porous polymer membrane |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH02180624A true JPH02180624A (en) | 1990-07-13 |
Family
ID=11476887
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP55289A Pending JPH02180624A (en) | 1989-01-06 | 1989-01-06 | Manufacturing method of porous polymer membrane |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02180624A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005525926A (en) * | 2002-05-17 | 2005-09-02 | ミリポア・コーポレイション | High throughput asymmetric membrane |
| JP2007154153A (en) * | 2005-11-10 | 2007-06-21 | Sumitomo Electric Fine Polymer Inc | Fluoroplastic porous membrane |
| WO2007140752A1 (en) * | 2006-06-06 | 2007-12-13 | Eads Deutschland Gmbh | Micromechanical filter for microparticles, in particular for pathogenic bacteria and viruses, and also process for production thereof |
| US7942274B2 (en) | 2000-05-24 | 2011-05-17 | Millipore Corporation | High-throughput asymmetric membrane |
| JP2011225894A (en) * | 2005-11-10 | 2011-11-10 | Sumitomo Electric Fine Polymer Inc | Fluororesin porous membrane |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS523987A (en) * | 1975-06-27 | 1977-01-12 | Kondo Seisakusho:Kk | Hydraulic drive device |
| JPS57140608A (en) * | 1981-02-25 | 1982-08-31 | Nitto Electric Ind Co Ltd | Gas separation film |
| JPS59117546A (en) * | 1982-12-25 | 1984-07-06 | Nissin Electric Co Ltd | Manufacture of porous polymeric film |
-
1989
- 1989-01-06 JP JP55289A patent/JPH02180624A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS523987A (en) * | 1975-06-27 | 1977-01-12 | Kondo Seisakusho:Kk | Hydraulic drive device |
| JPS57140608A (en) * | 1981-02-25 | 1982-08-31 | Nitto Electric Ind Co Ltd | Gas separation film |
| JPS59117546A (en) * | 1982-12-25 | 1984-07-06 | Nissin Electric Co Ltd | Manufacture of porous polymeric film |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7942274B2 (en) | 2000-05-24 | 2011-05-17 | Millipore Corporation | High-throughput asymmetric membrane |
| JP2005525926A (en) * | 2002-05-17 | 2005-09-02 | ミリポア・コーポレイション | High throughput asymmetric membrane |
| JP2010142806A (en) * | 2002-05-17 | 2010-07-01 | Millipore Corp | High-throughput asymmetrical membrane |
| JP2007154153A (en) * | 2005-11-10 | 2007-06-21 | Sumitomo Electric Fine Polymer Inc | Fluoroplastic porous membrane |
| JP2011225894A (en) * | 2005-11-10 | 2011-11-10 | Sumitomo Electric Fine Polymer Inc | Fluororesin porous membrane |
| WO2007140752A1 (en) * | 2006-06-06 | 2007-12-13 | Eads Deutschland Gmbh | Micromechanical filter for microparticles, in particular for pathogenic bacteria and viruses, and also process for production thereof |
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